CN104342783A - A nanometer or nanometer porous carbon fiber bundle, a preparing method thereof and applications of the bundle - Google Patents
A nanometer or nanometer porous carbon fiber bundle, a preparing method thereof and applications of the bundle Download PDFInfo
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- CN104342783A CN104342783A CN201310329335.3A CN201310329335A CN104342783A CN 104342783 A CN104342783 A CN 104342783A CN 201310329335 A CN201310329335 A CN 201310329335A CN 104342783 A CN104342783 A CN 104342783A
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Abstract
A preparing method of a nanometer or nanometer porous carbon fiber bundle is disclosed. The method includes following steps of: (1) suspending precursor fiber prepared by a solution or a melt containing spinnable polymer through electrostatic spinning into a liquid carrying plate; (2) extracting the precursor fiber in the liquid carrying plate at a speed of 5-60 r/min and winding the precursor fiber onto a fiber taking shaft to obtain a continuous directionally arranged precursor fiber bundle; and (3) heating the precursor fiber bundle by sections and charing. The method integrates electrostatic spinning, continuous wiredrawing and heating and charing, and obtains the continuous nanometer or nanometer porous carbon fiber bundle. The diameter, the length and the microstructure of the obtained nanometer or nanometer porous carbon fiber bundle are controllable. The nanometer or nanometer porous carbon fiber bundle prepared by the method shows good electrochemical performance when being applied in the field of energy storage devices, especially as an electrode material of supercapacitors.
Description
Technical field
The present invention relates to the preparation method of a kind of nanometer or nanoporous carbon fiber bundle, the nanometer prepared by the method or nanoporous carbon fiber bundle, and this nanometer or the application of nanoporous carbon fiber bundle in energy storage device.
Background technology
In recent years to flexible/wearable energy storage device (1.Koroneos, C., Spachos, T. & Moussiopoulos, N.Exergy analysis of renewable energy sources.Renewable Energy28,295-310, (2003); 2.Shim, B.S., Chen, W., Doty, C., Xu, C. & Kotov, N.A.Smart Electronic Yarns and Wearable Fabrics for Human Biomonitoring made by Carbon Nanotube Coating with Polyelectrolytes.Nano Letters8,4151-4157, (2008); 3.Park, S. & Jayaraman, S.Smart Textiles:Wearable Electronic Systems.MRS Bulletin28,585-591,) and the flexible energy storage device (4.Wang of the line style that can weave (2003), K., Meng, Q., Zhang, Y., Z.W. & Miao*, M.High-Performance Two-Ply Yarn Supercapacitors Based on Carbon Nanotubes and Polyaniline Nanowire Arrays.Advanced Materials, (2013); 5.Lee, J.A.et al.Ultrafast charge and discharge biscrolled yarn supercapacitors for textiles and microdevices.Nat Commun4, (2013); 6.Dalton, A.B.et al.Super-tough carbon-nanotube fibres.Nature423,703-703, (2003) .) research receive extensive concern.Therefore, preparation line style, flexibility, the electrode material of bent energy storage device as ultracapacitor become the most important thing.
Carbon fiber is the fibrous carbon material that organic fiber or low molecular hydrocarbons gas raw material are formed after charing process, carbon content is more than 90%, there is the good characteristics such as high strength, low-density, resistance to chemical attack, low resistance, be widely used in fields such as energy storage device, aerospace industry, aircraft industry.And the carbon fiber bundle be made up of carbon fiber is because having good flexibility and the chemical property of excellence, the electrode material of line style flexible super capacitor can be used as.
The method being commonly used to prepare carbon fiber bundle has chemical vapour deposition technique and method of electrostatic spinning.
Although chemical vapour deposition technique can produce carbon nano pipe array and therefrom wire drawing to form continuous print carbon fiber bundle (7.Jiang, K., Li, Q. & Fan, S.Nanotechnology:Spinning continuous carbon nanotube yarns.Nature419,801-801, (2002) .), but the carbon fiber bundle obtained often containing metallic catalyst, is difficult to remove completely; And only have so-called " super in-line arrangement " carbon nano pipe array just can pull out superior in quality carbon fiber bundle; And the diameter of wire drawing fiber can not control easily; Further, this complex process equipment, cost are high, and condition is harsh, are difficult to the carbon fiber bundle that extensive preparation is pure continuously.
At present, fibre bundle prepared by electrostatic spinning be macromolecular fibre bundle (8.Smit, E.,
u. & Sanderson, R.D.Continuous yarns from electrospun fibers.Polymer46,2419-2423, (2005); 9.Teo, W.-E., Gopal, R., Ramaseshan, R., Fujihara, K. & Ramakrishna, S.A dynamic liquid support system for continuous electrospun yarn fabrication.Polymer48,3400-3405, (2007) .), not yet there is electrospun polymer fibers bundle to carbonize the research forming carbon nano-fiber bundle or nanoporous carbon fiber bundle again through continuous spinning.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of nanometer or nanoporous carbon fiber bundle, electrostatic spinning, continuous wire drawing and heating charing combine by the method, not only can obtain continuous print nanometer or nanoporous carbon fiber bundle, and the diameter of the nanometer for preparing of the method or nanoporous carbon fiber bundle, length and microstructure are controlled, and the nanometer to be prepared by the method or nanoporous carbon fiber bundle are being applied to the electrode material especially as ultracapacitor in energy storage device field, presenting good chemical property.
To achieve these goals, the invention provides the preparation method of a kind of nanometer or nanoporous carbon fiber bundle, the method comprises the following steps: (1) can spin high molecular solution by containing or molten mass is suspended in liquid phase undertaking screen by precursor prepared by electrostatic spinning; (2) extract described liquid phase with the speed of 5-60 rev/min and accept precursor in screen and by this gray filament winding to getting a raw tow axle obtaining continuous print and align; (3) by described raw tow heat stepwise charing process.
Present invention also offers the nanometer or nanoporous carbon fiber bundle prepared by said method, the diameter of described carbon nano-fiber bundle is 20-300 micron, and length is 0.005-100 rice, and specific area is 10-1000 meters squared per gram.
In addition, present invention also offers described nanometer or the application of nanoporous carbon fiber bundle in energy storage device.
The nano wire that the present invention mainly utilizes electrostatic spinning technique to prepare, the diameter of nano wire bundle can be regulated and controled by changing the speed extracting the precursor that liquid phase is accepted in screen, the aperture of carbon nano-fiber can be regulated and controled by changing the kind can spinning Polymer Solution, and the distributional pattern of nano wire can be regulated and controled by changing liquid phase undertaking screen and align degree, make the nanometer of preparation or the diameter of nanoporous carbon fiber bundle and microstructure controlled; And the nanometer prepared by method of the present invention or nanoporous carbon fiber bundle can be applied to the electrode material especially as ultracapacitor in energy storage device field, present good chemical property; And preparation method's technique of the present invention is simple, cost is low, and electrostatic spinning, continuous wire drawing and heating charing being combined becomes a continuous print technique.
Other features and advantages of the present invention are described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for description, is used from explanation the present invention, but is not construed as limiting the invention with detailed description of the invention one below.In the accompanying drawings:
Fig. 1 is the schematic diagram of preparation nanometer of the present invention or nanoporous carbon fiber bundle;
Fig. 2 is the SEM figure of the carbon nano-fiber bundle according to embodiment of the method 1 preparation of the present invention;
Fig. 3 is the TEM figure of the carbon nano-fiber bundle according to embodiment of the method 1 preparation of the present invention;
Fig. 4 is the photo of prepared according to the methods of the invention carbon nano-fiber bundle bending state in line style flexible super capacitor;
Fig. 5 is the cyclic voltammetry curve of the carbon nano-fiber bundle according to embodiment of the method 1 preparation of the present invention;
Fig. 6 is the constant current charge-discharge curve of the carbon nano-fiber bundle according to embodiment of the method 1 preparation of the present invention;
Fig. 7 is the cyclic voltammetry curve of the nanoporous carbon fiber bundle according to embodiment of the method 7 preparation of the present invention;
Fig. 8 is the constant current charge-discharge curve of the nanoporous carbon fiber bundle according to embodiment of the method 7 preparation of the present invention.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides the preparation method of a kind of nanometer or nanoporous carbon fiber bundle, wherein, the method comprises the following steps: (1) can spin high molecular solution by containing or molten mass is suspended in liquid phase undertaking screen by precursor prepared by electrostatic spinning; (2) extract described liquid phase with the speed of 5-60 rev/min and accept precursor in screen and by this gray filament winding to getting a raw tow axle obtaining continuous print and align; (3) by described raw tow heat stepwise charing process.
According to the present invention, described spin macromolecule can be any can by electrostatic spinning technique by nano wire bundle be formed be suspended in liquid phase accept screen in macromolecule, under preferable case, can be one or more in polyacrylonitrile, polymethacrylates, polyvinylpyrrolidone, polyvinyl alcohol, polystyrene and PLA, be preferably one or more in polyacrylonitrile, polymethacrylates and polyvinylpyrrolidone.
According to the present invention, preferably, the method also comprises inorganic matter, inorganic nano-particle, one or more in organo-metallic compound are dispersed in described can spinning in high molecular solution or molten mass and are mixed with containing organic/inorganic substance, inorganic nano-particle, one or more spun macromolecule mixed solution in organo-metallic compound or molten mass, count in mass ratio, described inorganic matter, inorganic nano-particle, one or more total amount in organo-metallic compound and the described mass ratio spinning high molecular solution or molten mass are 0.001-0.5:1, be preferably 0.05-0.5:1.According to this preferred embodiment, pore structure and the diameter of nanometer or nanoporous carbon fiber bundle better can be regulated and controled.
According to the present invention, described inorganic matter, inorganic nano-particle, organo-metallic compound are not particularly limited, as long as can with can spin high molecular solution or molten mass without being obviously separated, wherein, described inorganic matter can for dissolving in the various inorganic salts in Polymer Solution, described inorganic matter can be one or more in metallic salt and nonmetal salt, be preferably chlorate, carbonate, one or more in acetate, be more preferably one or more in sodium chloride, manganese chloride, nickel acetate; Described inorganic nano-particle can be one or more in various metal, metal oxide nanoparticles and nonmetal oxide nano particle, is preferably tin oxide, manganese oxide, iron oxide, nickel oxide, zinc oxide (ZnO), alundum (Al2O3) (Al that granularity is 30-100nm
2o
3), silica (SiO
2) in one or more, be more preferably the silica that granularity is 30-100nm; Described organo-metallic compound can be the various organo-metallic compound that can dissolve each other with spinning Polymer Solution or melt, is preferably one or more in lead tetraethide, triphenyltin and three carbonyl cyclopentadiene manganese.
According to the present invention, the described macromolecule that spins can dissolve to be mixed with in a solvent and can spin high molecular solution, also can by can spin macromolecule melting be prepared into can form nano wire bundle by electrostatic spinning technique spin high molecular molten mass, wherein, high molecular solvent can be spun for dissolving to be not particularly limited, described solvent can form the described solvent that can spin high molecular solution for spinning macromolecule described in any can dissolving, can be such as one or more in DMF, ethanol, distilled water, oxolane and chloroform; And in mass ratio, described containing spinning macromolecule: organic solvent=1:4-13, be preferably 1:9-11.
According to the present invention, first, on described liquid phase undertaking screen, precursor is prepared by electrostatic spinning.Generally comprise high voltage source for the electrostatic spinning apparatus of electrostatic spinning in the present invention, liquid phase accepts screen, can spin the glass tube of high molecular solution or molten mass for splendid attire, wherein, one end of described glass tube is with the metal needle of 0.1-1.2mm, be preferably the metal needle of 0.2-0.7mm, the other end semi-closed state that can be opening-wide state also can be with an import, the size of described import is not particularly limited; It can be ethanol, distilled water or their mixed solution that described liquid phase accepts screen; The positive pole of described high voltage source is electrically connected with described metal needle, and negative pole and the liquid phase of described high voltage source are accepted to shield and be electrically connected.
Fig. 1 shows the preparation process schematic diagram according to a kind of nanometer of the present invention or nanoporous carbon fiber bundle.As shown in Figure 1:
First utilizing electrostatic spinning technique precursor to be suspended in liquid phase accepts in screen, this electrospinning process comprises can spin high molecular solution or molten mass is placed in glass tube, again the positive pole of high voltage source is electrically connected with metal needle, negative pole and liquid phase are accepted to shield and are electrically connected, open high voltage source and start electrostatic spinning apparatus, like this, high voltage electric field is formed between the metal needle and liquid phase undertaking screen of glass tube, spin high molecular solution or molten mass in glass tube are ejected by metal needle and form unordered and/or orderly nano wire, under the traction of electric field force, be suspended in liquid phase accept screen in and this liquid phase accept screen in form the tunica fibrosa be made up of precursor, wherein, the voltage of described high voltage source is 15-25kV, be preferably 15-20kV, it is 10-25cm that described nozzle and liquid phase accept the distance of shielding, and is preferably 12-20cm, spinning head quantity is at least 1, and single spinning head rate of extrusion is 0.1-2 ml/hour.
And then utilize continuous wire drawing technology to extract described liquid phase to accept precursor in screen and by this gray filament winding to getting a raw tow axle obtaining continuous print and align; Wherein, in continuous wire drawing process, the selection of extraction speed is extremely important, in the present invention, the speed extracted can be 5-60 rev/min, is preferably 10-50 rev/min, if the speed of extraction is lower than 5 revs/min or higher than 60 revs/min, the precursor of extraction then can be caused discontinuous, and extraction can occur, and out precursor maybe may by phenomenons such as precursor pump off.
Finally, again by described raw tow heat stepwise charing process, wherein, in heat stepwise charing processing procedure, the selection of carbonization temperature and time is also very important, in the present invention, described heat stepwise charing process comprises the following steps: (1) is at 200-400 DEG C of preliminary treatment 0.1-10 hour; (2) at 400-800 DEG C of process 0.1-10 hour; (3) at 800-1000 DEG C of heat treatment 0.1-10 hour; (4) at 1000-1500 DEG C of heat treatment 0.1-10 hour; Preferably, described heat stepwise charing process comprises the following steps: (1) is at 250-350 DEG C of preliminary treatment 0.5-8 hour; (2) at 350-750 DEG C of process 0.5-8 hour; (3) at 750-950 DEG C of heat treatment 0.5-8 hour; (4) at 950-1400 DEG C of heat treatment 0.5-8 hour; If the temperature that carbonization temperature or carbonization time limit lower than the present invention, then can cause charing not exclusively, if the temperature that carbonization temperature or carbonization time limit higher than the present invention, then can cause charing excessively, and then cause carbonizing the nanometer that obtains or nanoporous carbon fiber flexible declines.
According to the present invention, described liquid phase is accepted screen and is made up of the liquid solution immiscible with precursor, namely described liquid phase accept screen for spun the immiscible solution phase of macromolecular fibre, in the present invention, described liquid phase accepts that shield can preferably by ethanol, distilled water or their mixed solution; Be preferably distilled water.
According to a kind of detailed description of the invention of the present invention, this preparation method specifically comprises the following steps:
(1) macromolecule dissolution can be spun be mixed with in organic solvent and can spin Polymer Solution or molten mass, and in mass ratio, can macromolecule be spun: organic solvent=1:4-13;
(2) the spun Polymer Solution of preparation in step (1) or molten mass are placed in the glass tube of the nozzle other end with an import that there is 0.1-1.2mm an one end;
(3) fixing being equipped with the glass tube that can spin high molecular solution or molten mass in step (2), making the nozzle of described glass tube and horizontal line or vertical line be 35-49.5 degree;
(4) positive pole of metal needle with the high voltage source of 15-25kV is connected, liquid phase is accepted screen and is connected with the negative pole of the high voltage source of 15-25kV;
(5) accept in the liquid phase apart from described glass tube 10-25cm place the tunica fibrosa formed by unordered and/or orderly nano wire collecting preparation in screen;
(6) precursor in the tunica fibrosa obtained with the speed extraction step (5) of 10-50 rev/min and by this gray filament winding to getting a raw tow axle obtaining continuous print and align;
(7) described raw tow heat stepwise charing process step (6) obtained, wherein, the temperature and time of heat stepwise charing process is described above.
Preparation in accordance with the present invention, wherein, under preferable case, the method also comprise one or more in inorganic matter, inorganic nano-particle, organo-metallic compound are dispersed in described can spin in Polymer Solution to be mixed with can spin macromolecule mixed solution or molten mass containing described in one or more in organic/inorganic substance, inorganic nano-particle, organo-metallic compound.One or more nanometer in the inorganic matter contained formed, inorganic nano-particle, organo-metallic compound or the preparation method of nanoporous carbon fiber bundle are prepared according to a kind of method utilizing electrostatic spinning technique to prepare nano wire of the present invention, difference spins that fractionated polymer is loose replaces with first that to spin fractionated polymer loose in a solvent by described in a solvent by described, one or more in inorganic matter, inorganic nano-particle, organo-metallic compound are dispersed in described can spinning in Polymer Solution, namely this preparation method specifically comprises the following steps again:
(1) spin macromolecule dissolution in organic solvent by described, and in mass ratio, can macromolecule be spun: organic solvent=1:4-13; Again one or more in inorganic matter, inorganic nano-particle, organo-metallic compound are dispersed in described can spinning in Polymer Solution, and count in mass ratio, total amount and the described mass ratio spinning high molecular solution or molten mass of described inorganic matter, inorganic nano-particle, organo-metallic compound are 0.001-0.5:1, are mixed with containing one or more the spun Polymer Solution in organic/inorganic substance, inorganic nano-particle, organo-metallic compound or molten mass;
(2) be placed in containing one or more the spun Polymer Solution in organic/inorganic substance, inorganic nano-particle, organo-metallic compound or molten mass the glass tube of the metal needle other end with an import that there is 0.1-1.2mm an one end by what prepare in step (1);
(3) glass tube spinning high molecular solution or molten mass be equipped with containing one or more in organic/inorganic substance, inorganic nano-particle, organo-metallic compound in step (2) is fixed, make the nozzle of described glass tube and horizontal line or vertical line be 35-49.5 degree;
(4) high voltage source is spun high molecular solution with described or molten mass is electrically connected, then the positive pole of metal needle with the high voltage source of 15-25kV is connected, liquid phase is accepted screen and is connected with the negative pole of the high voltage source of 15-25kV;
(5) accept in the liquid phase apart from described glass tube 10-25cm place the tunica fibrosa formed by unordered and/or orderly nano wire collecting preparation in screen;
(6) precursor in the tunica fibrosa obtained with the speed extraction step (5) of 5-60 rev/min and by this gray filament winding to getting a raw tow axle obtaining continuous print and align;
(7) described raw tow heat stepwise charing process step (6) obtained, wherein, the temperature and time of heat stepwise charing process is described above.
Present invention also offers a kind of nanometer of being prepared by said method or nanoporous carbon fiber bundle, wherein, the diameter of described carbon nano-fiber bundle is 20-300 micron, and length is 0.005-100 rice, and specific area is 10-1000 meters squared per gram.
The nanometer prepared according to preparation method of the present invention or the application of nanoporous carbon fiber bundle in energy storage device.
Below will be described in detail the present invention by embodiment.In following examples, the model of high voltage source is SPELLMAN SL50/P60, purchased from American SPELLMAN company; Cold field emission scanning electronic microscope (Hitachi S4800) observes the diameter of nanometer prepared by the present invention or nanoporous carbon fiber bundle; Described polyacrylonitrile is purchased from alfa aesar, and number-average molecular weight is 160000; Described polyvinyl alcohol available from Sigma, number-average molecular weight 7600; Described polyvinylpyrrolidone available from Sigma, mean molecule quantity is 13000.
Utilize cyclic voltammetry and galvanostatic charge/discharge to study its chemical property, utilize constant current charge-discharge curve to calculate the ratio capacitance value of ultracapacitor.
Wherein, cyclic voltammetry Bio-Logic electrochemical workstation is tested, and voltage scan range is 0 ~ 1 volt, and sweep speed is 50 millivolts/second.
The concrete operation method of galvanostatic charge/discharge is as follows:
Adopt Bio-Logic electrochemical workstation to carry out constant current charge-discharge test to it ultracapacitor of assembling, its test voltage is 0-1 volt, and measuring current density is 1 microampere/centimetre.The ratio capacitance computing formula of ultracapacitor is:
In formula: C
lfor the ratio capacitance (millifarad/centimetre) of ultracapacitor;
I is discharge current (milliampere);
Δ t is the time (second) in discharge process;
Δ V is the potential difference (volt) in discharge process;
L is the length (centimetre) of ultracapacitor.
Embodiment 1
At 80 DEG C, by polyacrylonitrile in mass ratio 1:9 be dissolved in DMF the DMF solution being mixed with polyacrylonitrile.Then electrostatic spinning is carried out, wherein the consumption of solution is 1mL, the metal needle diameter of glass tube is 0.7mm, and the metal needle of this glass tube and horizontal line are 35.9 degree tilts, the voltage of high voltage source is 15kV, it is distilled water that this liquid phase accepts screen, and it is 15cm that spinning-nozzle and liquid phase accept the distance of shielding, and nozzle rate of extrusion is 1 ml/hour; Be suspended in after liquid phase accepts and form tunica fibrosa in screen until the precursor prepared by electrostatic spinning, extract described liquid phase with the speed of 50 revs/min and accept precursor in screen and by this gray filament winding to getting a raw tow axle obtaining continuous print and align; Then, by described raw tow heat stepwise charing process: (1) was 350 DEG C of preliminary treatment 0.5 hour; (2) 750 DEG C of process 0.5 hour; (3) 950 DEG C of heat treatments 0.5 hour; (4) 1400 DEG C of heat treatments 0.1 hour.It is 20 microns that result obtains average diameter, and average length is 10 meters, and average specific surface area is the continuous carbon nano-fiber bundle of 10 meters squared per gram.
Embodiment 2
Prepare carbon nano-fiber bundle according to the method identical with embodiment 1, difference extracts described liquid phase with the speed of 10 revs/min to accept the precursor in shielding.It is 300 microns that result obtains average diameter, and average length is 5 centimetres, and average specific surface area is the continuous carbon nano-fiber bundle of 10 meters squared per gram.
Embodiment 3
Prepare carbon nano-fiber bundle according to the method identical with embodiment 1, difference extracts described liquid phase with the speed of 20 revs/min to accept the precursor in shielding.It is 200 microns that result obtains average diameter, and average length is 0.005 meter, and average specific surface area is the continuous carbon nano-fiber bundle of 10 meters squared per gram.
Embodiment 4
Carbon nano-fiber bundle is prepared according to the method identical with embodiment 1, difference is that polyacrylonitrile, polymethacrylates are dissolved in N, polyacrylonitrile, polymethacrylates and N is mixed with in dinethylformamide, the mixed solution of dinethylformamide, and in mass ratio, polyacrylonitrile: polymethacrylates: DMF=1:1:9.It is 80 microns that result obtains average diameter, and average length is 62 centimetres, and average specific surface area is the continuous carbon nano-fiber bundle of 1000 meters squared per gram.
Embodiment 5
Prepare carbon nano-fiber bundle according to the method identical with embodiment 1, difference is the spun macromolecule in electrostatic spinning is polyvinylpyrrolidone.It is 10 microns that result obtains average diameter, and average length is 4 meters, and average specific surface area is the continuous carbon nano-fiber bundle of 60 meters squared per gram.
Embodiment 6
Carbon nano-fiber bundle is prepared according to the method identical with embodiment 1, difference is by different for the temperature and time of described raw tow heat stepwise charing process, in this embodiment, by the temperature and time of described raw tow heat stepwise charing process be: (1) was 250 DEG C of preliminary treatment 8 hours; (2) 350 DEG C of process 8 hours; (3) 750 DEG C of heat treatments 8 hours; (4) 950 DEG C of heat treatments 8 hours.It is 17 microns that result obtains average diameter, and average length is 8 meters, and average specific surface area is the continuous carbon nano-fiber bundle of 30 meters squared per gram.
Embodiment 7
Prepare carbon nano-fiber bundle according to the method identical with embodiment 1, difference be electrostatic spinning raw material solution by polyvinylpyrrolidone, polymethyl methacrylate, DMF in mass ratio 1:1:9 form.It is 8 microns that result obtains average diameter, and average length is 3.5 meters, and average specific surface area is the continuous nano-porous carbon fiber bundle of 180 meters squared per gram.
Embodiment 8
Prepare carbon nano-fiber bundle according to the method identical with embodiment 1, difference be electrostatic spinning raw material solution by polyvinylpyrrolidone, polymethyl methacrylate, DMF in mass ratio 1:0.5:9 form.It is 8 microns that result obtains average diameter, and average length is 3.5 meters, and average specific surface area is the continuous nano-porous carbon fiber bundle of 120 meters squared per gram.
Embodiment 9
Prepare carbon nano-fiber bundle according to the method identical with embodiment 1, difference be electrostatic spinning raw material solution by polymethyl methacrylate, DMF in mass ratio 1:9 form.It is 5 microns that result obtains average diameter, and average length is 1.5 meters, and average specific surface area is the continuous nano-porous carbon fiber bundle of 25 meters squared per gram.
Embodiment 10
Prepare carbon nano-fiber bundle according to the method identical with embodiment 1, difference be electrostatic spinning raw material solution by polyacrylonitrile, polymethyl methacrylate, DMF in mass ratio 1:1:9 form.It is 18 microns that result obtains average diameter, and average length is 7 meters, and average specific surface area is the continuous nano-porous carbon fiber bundle of 190 meters squared per gram.
Embodiment 11
Prepare carbon nano-fiber bundle according to the method identical with embodiment 1, difference be electrostatic spinning raw material solution by polyacrylonitrile, polymethyl methacrylate, DMF in mass ratio 1:0.5:9 form.It is 18 microns that result obtains average diameter, and average length is 7 meters, and average specific surface area is the continuous nano-porous carbon fiber bundle of 110 meters squared per gram.
Embodiment 12
Prepare carbon nano-fiber bundle according to the method identical with embodiment 1, difference be electrostatic spinning raw material solution by polyacrylonitrile, manganese chloride, DMF in mass ratio 1:1:9 form.It is 20 microns that result obtains average diameter, and average length is 10 meters, and average specific surface area is the continuous nano-sized carbon/manganese chloride fibre bundle of 30 meters squared per gram.
Embodiment 13
Prepare carbon nano-fiber bundle according to the method identical with embodiment 1, difference be electrostatic spinning raw material solution by polyacrylonitrile, zinc oxide, DMF in mass ratio 1:1:9 form.It is 20 microns that result obtains average diameter, and average length is 10 meters, and average specific surface area is the continuous nano-sized carbon/zinc oxide fiber bundle of 20 meters squared per gram.
Embodiment 14
Prepare carbon nano-fiber bundle according to the method identical with embodiment 1, difference be electrostatic spinning raw material solution by polyacrylonitrile, triphenyltin, DMF in mass ratio 1:1:9 form.It is 20 microns that result obtains average diameter, and average length is 10 meters, and average specific surface area is the continuous nano-sized carbon/tin fibre bundle of 60 meters squared per gram.
Embodiment 15
Prepare carbon nano-fiber bundle according to the method identical with embodiment 1, difference is this liquid phase undertaking screen is ethanol.It is 20 microns that result obtains average diameter, and average length is 10 meters, and average specific surface area is the continuous carbon nano-fiber bundle of 10 meters squared per gram.
Comparative example 1
Prepare carbon nano-fiber bundle according to the method identical with embodiment 1, difference extracts described liquid phase with the speed of 70 revs/min to accept the precursor in shielding.It is 10 microns that result obtains average diameter, and average length is 0.001 meter, and average specific surface area is 5 meters squared per gram, and obtains being not easy continuous print carbon nano-fiber bundle.
Comparative example 2
Prepare carbon nano-fiber bundle according to the method identical with embodiment 1, difference is: (1) was 100 DEG C of preliminary treatment 11 hours; (2) 300 DEG C of process 11 hours; (3) 700 DEG C of heat treatments 0.5 hour; (4) 1400 DEG C of heat treatments 0.5 hour.It is 20 microns that result obtains average diameter, and average length is 0.001 meter, and average specific surface area is 9 meters squared per gram, and obtains the flexible continuous carbon nano-fiber bundle reduced.
Comparative example 3
Prepare carbon nano-fiber bundle according to the method identical with embodiment 7, difference extracts described liquid phase with the speed of 4 revs/min to accept the precursor in shielding.It is 500 microns that result obtains average diameter, and average length is 1 meter, and average specific surface area is 7 meters squared per gram, and is not easy continuous print nanoporous carbon fiber bundle.
Comparative example 4
Prepare carbon nano-fiber bundle according to the method identical with embodiment 12, difference is: (1) was 100 DEG C of preliminary treatment 1 hour; (2) 300 DEG C of process 8 hours; (3) 700 DEG C of heat treatments 2 hours; (4) 1400 DEG C of heat treatments 0.5 hour.It is 18 microns that result obtains average diameter, and average length is 5 meters, and average specific surface area is 20 meters squared per gram, and the flexible continuous carbon nano-fiber bundle reduced.
Preparation example 1
Using the nanometer that obtains in embodiment 1-15 and comparative example 1-4 or nanoporous carbon fiber and nanometer/inorganic particulate carbon fiber reinforce plastic as the positive pole of ultracapacitor and negative pole, first two electrodes are connected with copper cash with conducting resinl respectively, be coated with respectively on two electrodes again and be covered with gel electrolyte, finally two electrodes enwind are assembled into line style flexible super capacitor together, as shown in Figure 4.Wherein, the preparation method of gel electrolyte is: add in 60 ml deionized water by 6 grams of polyvinyl alcohol, and 80 degrees Celsius are stirred to and dissolve completely, then add 6 grams of phosphoric acid, continues to be stirred to mix completely.
Test case 1
The line style flexible super capacitor assembled by preparation example 1 is carried out cyclic voltammetry and galvanostatic charge/discharge, and test result such as Fig. 5 is the cyclic voltammetry curve of the carbon nano-fiber bundle prepared by embodiment 1; As can be seen from the figure: the line style flexible super capacitor that preparation example 1 is assembled can normally work, but ratio capacitance is less; Fig. 6 is the constant current charge-discharge curve of the carbon nano-fiber bundle prepared by embodiment 1; As can be seen from the figure: the ultracapacitor that carbon nano-fiber bundle prepared by embodiment 1 is assembled into can normally work, but internal resistance is larger; Fig. 7 is the cyclic voltammetry curve of the nanoporous carbon fiber bundle prepared by embodiment 7; As can be seen from the figure: the ultracapacitor that nanoporous carbon fiber bundle prepared by embodiment 7 is assembled into can normally work, and ratio capacitance is larger than the ratio capacitance of preparation example 1; Fig. 8 is the constant current charge-discharge curve of the nanoporous carbon fiber bundle prepared by embodiment 7; As can be seen from the figure: the ultracapacitor that carbon nano-fiber bundle prepared by embodiment 7 is assembled into can normally work, and internal resistance is very little.
In addition, Fig. 2 is the SEM figure of the carbon nano-fiber bundle prepared by embodiment 1; As can be seen from the figure: this carbon nano-fiber beam diameter is homogeneous and continuous, and is made up of many carbon nano-fibers; Fig. 3 is the TEM figure of the carbon nano-fiber bundle prepared by embodiment 1; : the carbon nano-fiber smooth in appearance, the diameter that form this carbon nano-fiber bundle are homogeneous, and approximate solid as can be seen from the figure.
Result as can be seen from above embodiment 1-15, comparative example 1-4 and test case: the diameter that can regulate and control nano wire bundle by changing the speed extracting the precursor that liquid phase is accepted in screen, the aperture of carbon nano-fiber can be regulated and controled by changing the kind can spinning Polymer Solution, and the distributional pattern of nano wire can be regulated and controled by changing liquid phase undertaking screen and align degree, make the nanometer of preparation or the diameter of nanoporous carbon fiber bundle and microstructure controlled; And the nanometer prepared by method of the present invention or nanoporous carbon fiber bundle can be applied to the electrode material especially as ultracapacitor in energy storage device field, present good chemical property.
Claims (11)
1. a preparation method for nanometer or nanoporous carbon fiber bundle, the method comprises the following steps:
(1) be suspended in liquid phase by precursor prepared by electrostatic spinning accept in screen by containing high molecular solution or molten mass can be spun;
(2) extract described liquid phase with the speed of 5-60 rev/min and accept precursor in screen and by this gray filament winding to getting a raw tow axle obtaining continuous print and align;
(3) by described raw tow heat stepwise charing process.
2. method according to claim 1, wherein, the described macromolecule that spins is each family macromolecule that can be used for electrostatic spinning, is preferably one or more in polyacrylonitrile, polymethacrylates, polyvinylpyrrolidone, polyvinyl alcohol, polystyrene and PLA.
3. method according to claim 1 and 2, wherein, the method also comprises one or more in inorganic matter, inorganic nano-particle, organo-metallic compound to be dispersed in describedly can be spun in high molecular solution or molten mass, count in mass ratio, total amount and the described mass ratio spinning high molecular solution or molten mass of described inorganic matter, inorganic nano-particle, organo-metallic compound are 0.001-0.5:1.
4. the method according to claim 1 or 3, wherein, described inorganic matter is the various inorganic salts dissolved in Polymer Solution, is preferably one or more in sodium chloride, manganese chloride and nickel acetate; Described inorganic nano-particle is various metal and metal oxide nanoparticles, is preferably one or more in tin oxide, manganese oxide, iron oxide, nickel oxide, zinc oxide, alundum (Al2O3), silica; Described organo-metallic compound is the various organo-metallic compounds that can dissolve each other with spinning Polymer Solution or melt, is preferably one or more in lead tetraethide, triphenyltin and three carbonyl cyclopentadiene manganese.
5. the method according to claim 1 or 4, wherein, the method also comprises and is first prepared in organic solvent and described spin high molecular solution or spin macromolecule melting and be prepared into by described and can spin high molecular molten mass by the described macromolecule dissolution that spins, and in mass ratio, macromolecule can be spun: organic solvent=1:4-13, described organic solvent is one or more in DMF, ethanol, distilled water, oxolane and chloroform.
6. method according to claim 1, wherein, the condition of described electrostatic spinning comprises: supply voltage is 15-25kV, and the distance that described liquid phase is accepted between screen and nozzle is 10-25cm, spinning head quantity is at least 1, and single spinning head rate of extrusion is 0.1-2 ml/hour.
7. method according to claim 1, wherein, described liquid phase accept screen for spun the immiscible solution phase of macromolecular fibre, preferably ethanol, distilled water or their mixed solution.
8. method according to claim 1, wherein, extracts described liquid phase with the speed of 10-50 rev/min and accepts the precursor in shielding.
9. method according to claim 1, wherein, described heat stepwise charing process comprises the following steps: (1) is at 200-400 DEG C of preliminary treatment 0.1-10 hour; (2) at 400-800 DEG C of process 0.1-10 hour; (3) at 800-1000 DEG C of heat treatment 0.1-10 hour; (4) at 1000-1500 DEG C of heat treatment 0.1-10 hour; Preferably, described heat stepwise charing process comprises the following steps: (1) is at 250-350 DEG C of preliminary treatment 0.5-8 hour; (2) at 350-750 DEG C of process 0.5-8 hour; (3) at 750-950 DEG C of heat treatment 0.5-8 hour; (4) at 950-1400 DEG C of heat treatment 0.5-8 hour.
10. nanometer prepared by the method in claim 1-9 described in any one or nanoporous carbon fiber bundle, wherein, the diameter of described carbon nano-fiber bundle is 20-300 micron, and length is 0.005-100 rice, and specific area is 10-1000 meters squared per gram.
Nanometer prepared by the method in 11. claim 1-10 described in any one or the application of nanoporous carbon fiber bundle in energy storage device.
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Application publication date: 20150211 |